Phenyl azophenyl dyestuff

ABSTRACT

Dyestuff of the formula: ##SPC1## 
     In which m is equal to 0 or 1, n is equal to 1, 2 or 3, A represents the residue of an aromatic or heterocyclic diazotizable amine devoid of solubilizing acid groups, the benzene ring B is unsubstituted or substituted by one or two atoms of chlorine or bromine or methyl, ethyl, methoxy, ethoxy or acylamino groups, X represents a hydrogen or chlorine atom or a methyl, ethyl, methoxy, ethoxy or acylamino group, Y represents a hydrogen atom or a methyl, ethyl, methoxy or ethoxy group, R represents a hydrogen atom, a mono substituted or unsubstituted alkyl group or a group of the formula: ##SPC2## 
     And Z represents a 2-cyanovinyl, 2-cyanoethyl or 2-chloro-2-cyanoethyl residue; process for the preparation of dyestuffs of the above formula; process for coloring hydrophobic materials with such dyestuffs; hydrophobic materials colored with such dyestuffs and esters of the formula: ##SPC3## 
     Wherein m, n, A, B, R, X, Y and Z have the meanings given above.

The present invention relates to new azo compounds which are scarcely soluble in water and can be used as dispersion dyestuffs for dyeing and printing fibers or fibrous materials which are based on organic substances with high molecular weight, are hydrophobic and are wholly or partially synthetic.

According to the present invention dyestuffs are provided of the general formula: ##SPC4##

In which m is equal to 0 or 1, n is equal to 1, 2 or 3, preferably 2, A represents the residue of an aromatic or heterocyclic diazotisable amine devoid of any solubilising acid groups such as sulphonic or carboxylic groups, the benzene ring B is unsubstituted or substituted by one or two atoms of chlorine or bromine or methyl, ethyl, methoxy, ethoxy or acylamino groups, X represents a hydrogen or chlorine atom or a methyl, ethyl, methoxy, ethoxy or acylamino group, Y represents a hydrogen atom or a methyl, ethyl, methoxy or ethoxy group, R represents a hydrogen atom, a mono substituted or unsubstituted alkyl group, or a group of the formula: ##SPC5##

And Z represents a 2-cyano-vinyl residue, a 2-cyano-ethyl residue or a 2-chloro-2-cyano-ethyl residue fixed in the ortho, meta or para postion.

Examples of residue A are phenyl, naphthyl, thiazolyl, benzothiazolyl, benzisothiazolyl, thienyl, thiadiazolyl and imidazolyl. These residues may have from one to three substituents such as, for example, chlorine or bromine atoms or the nitro, cyano, thiocyano, acyl, carbalkoxy containing 2 to 5 carbon atoms or alkylsulphonyl groups containing 1 to 4 carbon atoms.

The alkyl group, which may be represented by R or which is part of the alkylsulphonyl groups possibly present on the A residue preferably contains 1 to 4 carbon atoms. The carbalkoxy group possibly present on the A residue preferably contains 2 to 5 carbon atoms.

The acyl residue of the acylamino groups which are possibly present on the B ring or may be represented by X, may be that of an aliphatic acid with a low molecular weight, such as for example formyl, acetyl or propanoyl, or that of an aromatic acid, for example benzoyl, or of an araliphatic acid, for example cinnamoyl.

The acetyl group may be mentioned more particularly as an acyl residue which is possibly present on the A residue.

The hydroxy, alkoxy containing one to four carbon atoms, phenoxy, acyloxy, especially acetyloxy, nitrile, alkylsulphonyl, containing 1 to 4 carbon atoms, carbalkoxy, containing 2 to 5 carbon atoms, alkoxycarbonyloxy groups containing 2 to 5 carbon atoms may be mentioned as possible substituents of the alkyl group which may be represented by R.

The dyestuffs of formula (I) may be prepared for example by coupling the diazo derivative of an amine of the formula: ##SPC6##

with an ester of the formula: ##SPC7##

or with an alcohol of the formula: ##SPC8##

and, in this latter case, subsequently esterifying the dyestuff thus obtained of the formula: ##SPC9##

for example by means of an acid chloride of the formula: ##SPC10##

In formulae (III) to (VII), m, n, A, B, R, X, Y and Z have the same meanings as given above.

The amine of formula (III) may be diazotised for example in a known manner by means of sodium nitrite in a hydrochloric or sulphuric medium or by means of nitrosyl sulphuric acid mixed with sulphuric acid or possibly a carboxylic acid such as acetic or propionic acid, at a temperature of approximately 0° C.

The coupling with the ester (IV) or with the alcohol (V) may also be effected for example in a known manner in a neutral or acid aqueous medium at a temperature of from 0° to 5° C.

The dyestuff of formula (VI) is preferably esterified by means of the acid chloride of formula (VII) in an inert organic solvent, in the presence of a proton acceptor such as for example pyridine, piperidine or a trialkyl amine such as triethyl amine. Examples of inert organic solvents are halogenated hydrocarbons such as methylene chloride, trichlorethylene or chlorobenzene, ketones such as acetone or methyl ethyl ketone and ethers such as diethyl ether, dioxan and methoxy benzene.

The esters of formula (IV) are new products and, as such, form part of the invention. They may be prepared for example, by esterifying the alcohol of formula (V) by means of an acid chloride of formula (VII) under the same conditions as those given above for the esterification of the dyestuffs of formula (VI).

The acid chlorides of formula (VII) may be prepared for example by reacting thionyl chloride with the corresponding acids of the formula: ##SPC11##

wherein Z has the same meaning as that given above.

The acids of formula (VIII), in which Z represents the 2-chloro 2-cyano ethyl residue (-CH₂ -CHCl-CN), may be prepared, for example, by the Meerwein reaction between acrylonitrile and the diazonium chloride of 2-,3- or 4-amino benzoic acid. By means of a dehydro halogenation process with an alkaline agent, the acids of formula (VIII) are then obtained, in which Z represents the 2-cyano vinyl residue. The acids of formula (VIII), in which Z represents the 2-cyano ethyl residue, may be obtained for example by reducing (2-chloro-2-cyano ethyl)-benzoic acids.

The new dyestuffs of formula (I), and more particularly those in which m is equal to zero, Y represents a hydrogen atom, X represents a hydrogen or chlorine atom or a methyl or acetylamino group, R represents an ethyl or β-cyanoethyl group and n is equal to 2, are remarkable disperse dyestuffs which are highly suitable for dyeing and printing fibres and fabrics based on aromatic polyesters or cellulose triacetate. Some of these dyestuffs are also suitable for dyeing cellulose diacetate and polyamides. Before they are used, it is recommended that they be converted into tinctorial prepartions, i.e. that they be pre-dispersed with dispersing agents such as soap, the residual lyes of sulphite cellulose, the products resulting from condensing naphthalene-sulphonic acids with formaldehyde, in particular the dinaphthyl-methane-disulphonate, the sulphonated esters of succinic acid, the products obtained by condensing cresols with formaldehyde and naphtholsulphonic acids.

Polyester fibres may be dyed in the presence of carriers at temperatures ranging from 80° to 125° C. or without a carrier under pressure between 100° and 140° C. They may also be foularded or printed with aqueous dispersions of the new dyestuffs which are then fixed at 140° to 220° C.

The dyestuffs of formula (I) have excellent affinity for these fibres which they dye in shades which are very fast, particularly to sublimation and light.

Compared with the close known dyestuffs of formula (I), in which the residue ##SPC12##

is replaced by an acetyl, benzoyl, p-chlorobenzoyl or cinnamoyl residue, the new dyestuffs of the invention generally have superior fastness to sublimation whilst retaining an excellent tinctorial affinity.

The invention is illustrated by the following Examples, in which the parts indicated are parts by weight unless otherwise mentioned.

EXAMPLE 1 Preparation of 2-(2-chloro-2-cyano ethyl) benzoic acid

274 parts of anthranilic acid are mixed with 650 parts of hydrochloric acid (density 1.15) and 560 parts of crystallizable acetic acid. The mixture is cooled externally to 0° C. by means of a brine, then diazotised by means of 138 parts of sodium nitrite. The solution of the diazo derivative is then poured, whilst being stirred, into a mixture of 190 parts of acetone and 370 parts of acrylonitrile, at the same time as a solution of 6 parts of cuprous chloride in 50 parts of hydrochloric acid (density 1.08). The reaction is exothermic. After the diazonium chloride has disappeared and after decantation and crystallization in water, 330 parts of a product are obtained which has a melting point of 116°-117° C. and which is recrystallized in xylene. 314 parts of 2-(2-chloro-2-cyanoethyl) benzoic acid are obtained. M.P.: 119°-120° C.

    ______________________________________                                         Elementary Analysis:                                                                            C %     H %     N %   Cl %                                    ______________________________________                                         Calculated for C.sub.10 H.sub.8 NO.sub.2 Cl                                                     57.28   3.82    6.68  16.95                                   Found            57.44   3.83    6.45  16.79                                   ______________________________________                                    

By operating in the same manner using 3-amino or 4-amino benzoic acids, the meta (M.P. 112°-113° C.) or para (M.P.: 160°-162° C.) isomers are obtained with yields of 65% and 85% respectively.

EXAMPLE 2 Preparation of 2-(2-chloro-2-cyanoethyl) benzoyl chloride

209.5 parts of 2-(2-chloro-2-cyanoethyl) benzoic acid are made into a paste in 220 parts of toluene and 125 parts of thionyl chloride and the mixture is refluxed until the acid completely dissolves. Then the surplus thionyl chloride and toluene are eliminated under reduced pressure. 2-(2-chloro-2-cyanoethyl) benzoyl chloride is obtained which is liquid at normal temperature.

By operating in the same manner using the meta or paraisomers of 2-(2-chloro-2-cyanoethyl) benzoic acid one obtains 3-(2-chloro-2-cyanoethyl) benzoyl chloride or 4-(2-chloro-2-cyanoethyl) benzoyl chloride respectively.

EXAMPLE 3 Preparation of 4-(2-cyanovinyl) benzoic acid

120 parts of potassium hydroxide are dissolved in 240 parts of methanol and this solution is poured slowly into a mixture of 209.5 parts of 4-(2-chloro-2-cyanoethyl) benzoic acid and 400 parts of methanol. The dehydrohalogenation reaction is very exothermic. Reflux is maintained for 30 minutes. The potassium salt of 4-(2-cyanovinyl) benzoic acid precipitates. It is filtered when cold and taken up in an acid medium to obtain the free acid. Thus, 160 parts of crude 4-(2-cyanovinyl) benzoic acid are obtained which are purified by sublimation under reduced pressure at about 190°-200° C. They are also sublimed under normal pressure at about 270° C.

    ______________________________________                                         Elementary Analysis:                                                                             C %      H %     N %                                         ______________________________________                                         Calculated for C.sub.10 H.sub.7 NO.sub.2                                                         69.36    4.05    8.09                                        Found             68.04    4.15    7.88                                        ______________________________________                                    

By operating in the same manner the ortho or meta isomers may be obtained.

EXAMPLE 4 Preparation of 4-(2-cyanovinyl) benzoyl chloride

17.3 parts of 4-(2-cyanovinyl) benzoic acid are made into a paste in 80 parts of thionyl chloride and the mixture is refluxed for 15 minutes. Then the surplus thionyl chloride is eliminated under reduced pressure and the 4-(2-cyanovinyl) benzoyl chloride, which is thus obtained, is purified by being recrystallized in xylene. M.P.: 154° C.

    ______________________________________                                         Elementary Analysis:                                                                           C %      H %     N %   Cl %                                    ______________________________________                                         Calculated for C.sub.10 H.sub.6 NCCl                                                           62.75    3.14    7.32  18.55                                   Found           63.07    3.18    7.33  18.22                                   ______________________________________                                    

The ortho and meta isomers are prepared in the same manner.

EXAMPLE 5 Preparation of 4-(2-cyanoethyl) benzoic acid

100 parts of zinc powder are gradually added to a solution of 209.5 parts of 4-(2-chloro-2-cyanoethyl) benzoic acid in 500 parts of glacial acetic acid. The temperature rises quickly up to reflux and is maintained for approximately 1 hour. The solution is filtered when hot so a to eliminate the insoluble matter, then the filtrate is diluted with 1000 parts of water and the precipitate formed is isolated. Thus 122 parts of 4-(2-cyanoethyl) benzoic acid are obtained. M.P.: 182° C.

    ______________________________________                                         Elementary Analysis:                                                                             C %      H %     N %                                         ______________________________________                                         Calculated for C.sub.10 H.sub.9 NO.sub.2                                                         68.57    5.14    8.00                                        Found             68.37    5.09    7.93                                        ______________________________________                                    

By operating in the same manner, the 2-(2-cyano ethyl) benzoic acid (ortho isomer) and the 3-(2-cyano ethyl) benzoic acid (meta isomer) may be prepared.

EXAMPLE 6 Preparation of 4-(2-cyanoethyl) benzoyl chloride

A mixture of 17.5 parts of 4-(2-cyanoethyl) benzoic acid and 120 parts of thionyl chloride are refluxed for 15 minutes. The surplus thionyl chloride is then eliminated under reduced pressure and the 4-(2-cyanoethyl) benzoyl chloride is obtained which is liquid at atmospheric temperature.

The ortho and meta isomers may be prepared in the same manner using the corresponding acids.

EXAMPLE 7

179 parts of N-ethyl N-hydroxyethyl metatoluidine are dissolved in 240 parts of acetone and 120 parts of triethylamine. 274 parts of 2-(2-chloro-2-cyanoethyl) benzoyl chloride are introduced gradually. The reaction is exothermic. The mixture is maintained at reflux for approximately 30 minutes. The ester of the formula: ##SPC13##

which is thus formed may be isolated by decantation in water. The reaction mixture may also be used as such for the subsequent coupling process.

EXAMPLE 8

0.7 parts of sodium nitrite is dissolved in 15 parts of sulphuric acid at 63° Be, then 1.63 parts of 2-amino-5-nitrobenzonitrile are introduced slowly. The solution of the diazo derivative is then poured onto 100 parts of ice and the excess nitrite is destroyed. A solution of 3.70 parts of the ester of formula (IX) in 25 parts of glacial acetic acid is then added gradually. The precipitate is filtered and rinsed until it is neutral.

In the dispersed form, the dyestuff thus obtained of the formula: ##SPC14##

has excellent affinity for polyester fibres which it dyes with a shade which is very fast to light and sublimation.

The following Table shows other Examples of dyestuffs according to the invention which have been prepared as in Example 8 by coupling the diazo derivative of the amine of formula (III) indicated in the second column with the ester of formula (IV) defined in the following columns and prepared by the method given in Example 7 using the corresponding alcohol of formula (V) and the corresponding acid chloride of formula (VII). In column Z, the letter o, m or p placed in front of the group represented by Z indicated the position (ortho, meta or para respectively) of Z relative to the ester group.

    __________________________________________________________________________                                                              Shade on                                Ester of formula (IV)                  polyester             Example                                                                             Amine of formula (III)                                                                      n Y    X     R                   Z     fibres                __________________________________________________________________________     9    2-amino-5-nitro-benzo-                                                                      2 H    CH.sub.3                                                                             C.sub.2 H.sub.5  p, CH.sub.2 CH(Cl)CN                                                                    ruby                       nitrile                                                                   10   "            " "    "     "                p, CH=CH--CN                                                                            "                     11   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    12   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    13   "            " "    "     "                m, CH.sub.2 CH(Cl)CN                                                                    "                     14   "            " "    NHCOCH.sub.3                                                                         "                o, CH.sub.2 CH(Cl)CN                                                                    reddish-                                                                       blue                  15   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     16   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    17   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    18   "            " "    Cl    "                o, CH.sub.2 CH(Cl)CN                                                                    red                   19   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     20   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    21   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    22   "            " OCH.sub.3                                                                           CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    violet                23   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     24   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    25   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                         nitrile                                                                   26   "            " "    NHCOCH.sub.3                                                                         "                o, CH.sub.2 CH(Cl)CN                                                                    blue                  27   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    28   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     29   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    30   "            " H    H     CH.sub.2 CH.sub.2 CN                                                                            o, CH.sub.2 CH(Cl)CN                                                                    red                   31   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    32   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     33   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    34   "            " "    benzoyl-                                                                             C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                    reddish-                                       amino                           blue                  35   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     36   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    37   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    38   "            " "    H     C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                    bluish-                                                                        red                   39   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     40   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    41   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    42   "            3 "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    ruby                  43   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    44   "            2 "    H     C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                        o, CH.sub.2 CH(Cl)CN                                                                    bluish-                                                                        red                   45   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    46   "            " "    Cl    CH.sub.2 CH.sub.2 CN                                                                            o, CH.sub.2 CH(Cl)CN                                                                    red                   47   "            " "    "     CH.sub.2 CH.sub.2 CN                                                                            p, CH.sub.2 CH.sub.2                                                                    "N                    48   "            " "    OCH.sub.3                                                                            "                o, CH.sub.2 CH(Cl)CN                                                                    bluish-                                                                        red                   49   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    50   "            " "    H     2-[2-(2-chloro-2-cyanoethyl)-                                                                   o, CH.sub.2 CH(Cl)CN                                                                    red                                                  benzoyloxy]-ethyl                               51   "            " "    "     2-[2-(2-cyanoethyl)-benzoyl-                                                                    o, CH.sub.2 CH.sub.2                                                                    "N                                                   oxyl]-ethyl                                     52   "            3 "    CH.sub.3                                                                             2-[4-(2-chloro-2-cyanoethyl)-                                                                   p, CH.sub.2 CH(Cl)CN                                                                    "                                                    benzoyloxy]-ethyl                               53   "            " "    "     2-[4-(2-cyano-ethyl)4-                                                                          p, CH.sub.2 CH.sub.2                                                                    "N                                                   benzoyloxy]-2-ethyl                             54   2-chloro-4-  " "    "     C.sub.2 H.sub.5  o, CH.sub.2 CH(Cl)CN                                                                    scarlet                    nitro-aniline                                                             55   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    56   "            2 "    "     "                p, CH=CHCN                                                                              "                     57   "            " "    NHCOCH.sub.3                                                                         "                o, CH.sub.2 CH(Cl)CN                                                                    bluish-                                                                        red                   58   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    59   "            " "    benzoyl-                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    "                                              amino                                                 60   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    61   "            " OCH.sub.3                                                                           NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    ruby                  62   2-bromo-4-nitro-                                                                            " H    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    scarlet                    aniline                                                                   63   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    64   "            " OCH.sub.3                                                                           NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    ruby                  65   "            " "    benzoyl-                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    "                                              amino                                                 66   2,6-dichloro-4-nitro-                                                                       " H    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    reddish                    aniline                                             brown                 67   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    68   "            " "    "     "                p, CH=CHCN                                                                              "                     69   "            " "    NHCOCH.sub.3                                                                         "                o, CH.sub.2 CH(Cl)CN                                                                    bordeaux              70   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    71   "            " OCH.sub.3                                                                           benzoyl-                                                                             p, CH.sub.2 CH.sub.2 CN                                                                         reddish-                                                amino                           violet                72   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     73   2,6-dibromo-4-nitro-                                                                        " H    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    reddish-                   aniline                                             brown                 74   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     75   "            " OCH.sub.3                                                                           NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    reddish-                                                                       violet                76   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     77   "            " "    benzoyl-                                                                             "                p, CH=CHCN                                                                              "                                              amino                                                 78   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     79   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    80   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    81   4-nitro-aniline                                                                             " H    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    scarlet               82   "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                    83   "            " "    NHCOCH.sub.3                                                                         "                o, CH.sub.2 CH(Cl)CN                                                                    red                   84   "            " "    NHCOCH.sub.3                                                                         "                p, CH=CHCN                                                                              "                     85   "            " "    benzoyl-                                                                             "                p, CH.sub.2 CH.sub.2                                                                    "N                                             amino                                                 86   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     87   "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    bluish-                                                                        red                   88   2,4-dinitro-6-bromo-                                                                        " H    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    violet                     aniline                                                                   89   "            " "    "     "                p, CH=CHCN                                                                              violet                90   "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                     91   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     92   "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    reddish                                                                        blue                  93   "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                     94   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    95   "            " "    benzoyl-                                                                             "                p, CH.sub.2 CH.sub.2                                                                    "N                                             amino                                                 96   "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                    97   "            " OCH.sub.3                                                                           NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    navy                                                                           blue                  98   "            " "    "     "                p, CH=CHCN                                                                              "                     99   2,4-dinitro-6-chloro-                                                                       " H    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    bluish-                    aniline                                             violet                 100 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     101 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    reddish-                                                                       blue                   102 "            " "    "     "                m, CH=CHCN                                                                              "                      103 "            " "    benzoyl-                                                                             "                o, CH.sub.2 CH.sub.2                                                                    "N                                             amino                                                  104 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     105 "            " OCH.sub.3                                                                           NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    navy blue              106 2-amino-3,5-dinitro-                                                           benzonitrile " H    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    reddish-                                                                       blue                   107 "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                      108 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    blue                   109 "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                      110 "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                      111 "            " "    benzoyl-                                                                             "                p, CH.sub.2 CH.sub.2                                                                    "N                                             amino-                                                 112 "            " OCH.sub.3                                                                           "     "                p, CH.sub.2 CH.sub.2                                                                    greenish-                                                                      blue                   113 "            " "    "     "                p, CH=CHCN                                                                              "                      114 4-amino-azobenzene                                                                          " H    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    orange                 115 "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                      116 "            " "    NHCOCH.sub.3                                                                         "                p, CH=CHCN                                                                              scarlet                117 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     118 "            " "    benzoyl-                                                                             "                m, CH.sub.2 CH.sub.2                                                                    "N                                             amino                                                  119 "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                      120 2-amino-5-nitro-                                                               thiazole     " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    reddish-                                                                       blue                   121 "            " "    "     "                p, CH.sub.2 CH(Cl)CN                                                                    "                      122 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     123 "            " "    "     "                p, CH=CHCN                                                                              "                      124 "            " "    "     "                o, CH.sub.2 CH.sub.2                                                                    "N                     125 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    blue                   126 "            " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    "                      127 "            " "    benzoyl-                                                                             "                p, CH.sub.2 CH.sub.2                                                                    "N                                             amino                                                  128 "            " "    "     "                m, CH.sub.2 CH(Cl)CNZ                                                                   "                      129 "            " OCH.sub.3                                                                           NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    greenish-                                                                      blue                   130 3-methyl-4-nitro-                                                              5-amino-isothiazole                                                                         " H    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    ruby                   131 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     132 2-amino-6-carbethoxy-                                                          benzothiazole                                                                               " "    "     "                o, CH.sub.2 CH(Cl)CN                                                                    red                    133 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    ruby                   134 "            " "    benzoyl-                                                                       amino "                p, CH.sub.2 CH.sub.2                                                                    "N                     135 2-amino-6-thiocyano-                                                           benzothiazole                                                                               " "    CH.sub.3                                                                             "                CH.sub.2 CH(Cl)CN                                                                       bluish-                                                                        red                    136 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    reddish-                                                                       violet                 137 "            " "    benzoyl-                                                                       amino "                m, CH=CHCN                                                                              "                      138 2-amino-6-methylsul-                                                                        " "    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    ruby                       fonyl-benzothiazole                                                        139 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    violet                 140 "            " "    benzoyl-                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    "                                              amino                                                  141 2-amino-6-cyano-                                                                            " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    red                        benzothiazole                                                              142 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    ruby                   143 "            " "    benzoyla-                                                                            "                p, CH.sub.2 CH.sub.2                                                                    "N                                             mino                                                   144 2-amino-6-nitro-benzo-                                                         thiazole     " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    bluish-                                                                        red                    145 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    violet                 146 "            " "    benzoyl-                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    "                                              amino                                                  147 2-methylsulfonyl-4-                                                            nitro-aniline                                                                               " "    CH.sub.3                                                                             "                m, CH.sub.2                                                                             rubyl)CN               148 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    violet                 149 "            " "    benzoyl-                                                                       amino "                p, CH.sub.2 CH.sub.2                                                                    "N                     150 2-chloro-4-methyl-                                                             sulfonyl-aniline                                                                            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH(Cl)CN                                                                    red                    151 2-nitro-4-methyl-                                                                           " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    "                          sulfonyl-aniline                                                           152 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    ruby                   153 3-amino-5-nitro-                                                               benzisothiazole-2,1                                                                         " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    blue                   154 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    greenish-                                                                      blue                   155 "            " "    benzoyl-                                                                       amino "                p, CH.sub.2 CH.sub.2                                                                    "N                     156 2-amino-5-nitro-                                                                            " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    scarlet                    thiadiazole-1,3,4                                                          157 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    red                    158 3-methylsulfonyl-5-amino                                                       thiadiazole-1,2,4                                                                           " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    "                      159 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    bluish-                                                                        red                    160 3-phenyl-5-amino-                                                              thiadiazole-1,2,4                                                                           " "    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    red                    161 "            " "    NHCOCH.sub.3                                                                         "                o, CH.sub.2 CH(Cl)CN                                                                    bluish-                                                                        red                    162 2-amino-3-chloro-5-                                                            nitro benzonitrile                                                                          " "    CH.sub.3                                                                             "                o, CH.sub.2 CH(Cl)CN                                                                    violet                 163 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    bluish-                                                                        violet                 164 2-amino-3-bromo-5-                                                             nitro benzonitrile                                                                          " "    CH.sub.3                                                                             "                p, CH=CHCN                                                                              violet                 165 "            " "    NHCOCH.sub.3                                                                         "                p, CH.sub.2 CH.sub.2                                                                    bluish-                                                                        violet                 166  2-carbethoxy-4-nitro-                                                         aniline      " "    "     "                p, CH.sub.2 CH.sub.2                                                                    ruby                   167 "            " "    CH.sub.3                                                                             "                p, CH.sub.2 CH.sub.2                                                                    red                    168 2-amino-5-nitro-benzo-                                                                      " "    H     C.sub.2 H.sub.4 OCO-                                                                            o, CH.sub.2 CH.sub.2                                                                    ruby                       nitrile                   CH.sub.3                                         169 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     170 "            " "    "     C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                               o, CH.sub.2 CH.sub.2                                                                    "N                     171 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     172 "            " "    "     C.sub.2 H.sub.4 OH                                                                              o, CH.sub.2 CH.sub.2                                                                    "N                     173 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     174 "            " "    "     C.sub.2 H.sub.4 OCH.sub.3                                                                       p, CH.sub.2 CH.sub.2                                                                    "N                     175 "            " "    "     C.sub.2 H.sub.4 SO.sub.2 -                                                     CH.sub.3         o, CH.sub.2 CH.sub.2                                                                    red                    176 "            " "    "     C.sub.2 H.sub.4 OCO.sub.2 -                                                                     o, CH.sub.2 CH.sub.2                                                                    ruby                                                 CH.sub.3                                         177 "            " "    "     phenoxy-         p, CH.sub.2 CH.sub.2                                                                    "N                                                   ethyl                                            178 2-amino-3-nitro-5-                                                                          " "    CH.sub.3                                                                             C.sub.2 H.sub.5  o, CH.sub.2 CH.sub.2                                                                    blue                       acetyl-thiophene                                                           179 "            " "    "     "                p, CH.sub.2 CH.sub.2                                                                    "N                     180 2-amino-5-nitro-                                                                            " OC.sub.2 H.sub.5                                                                    "     "                o, CH.sub.2 CH.sub.2                                                                    violet                     benzonitrile                                                               181 "            " CH.sub.3                                                                            "     "                o, CH.sub.2 CH.sub.2                                                                    ruby                   182 "            " C.sub.2 H.sub.5                                                                     H     "                  "      "                      183 "            " H    C.sub.2 H.sub.5                                                                      "                  "      "                      184 "            " "    OC.sub.2 H.sub.5                                                                     CH.sub.2 CH.sub.2 CN                                                                              "      bluish-                                                                        red                    185 "            " "    NH--CHO                                                                              C.sub.2 H.sub.5    "      reddish-                                                                       blue                   186 "            " "    NHCOC.sub.2 H.sub.5                                                                  "                  "      "                      187 "            " "    cinnamoyl-                                                                     amino "                  "      "                      188 3-chloro-4-amino-                                                                           " "    CH.sub.3                                                                             "                  "      scarlet                    azobenzene                                                                 189 3-bromo-amino-                                                                              " "    "     "                  "      "                          azobenzene                                                                 190 3,5-dichloro-4-amino-                                                                       " "    "     "                  "      reddish-                   azobenzene                                          brown                  191 3,5-dibromo-4-amino                                                                         " "    "     "                  "      "                          azobenzene                                                                 192 4-amino-2-methyl-                                                                           " "    "     "                  "      orange                     azobenzene                                                                 193 4-amino-2-ethyl-                                                                            " "    "     "                  "      "                          azobenzene                                                                 194 4-amino-2-methoxy-                                                                          " "    "     "                  "      reddish-                   azobenzene                                          orange                 195 4-amino-2-ethoxy-                                                                           " "    "     "                  "      "                          azobenzene                                                                 196 2,4-dinitro-6-chloro-                                                                       " "    "     "                  "      bluish-                    aniline                                             violet                 197 2,6-dichloro-4-nitro-                                                                       " "    "     "                  "      reddish-                   aniline                                                                   __________________________________________________________________________

EXAMPLE 198

5.5 parts of 2-cyano-4-nitro 2'-methyl-4'-[N-ethyl-N-(hydroxy-ethyl)amino] azobenzene, obtained by coupling the diazo derivative of 2-amino-5-nitrobenzonitrile with N-ethyl-N-hydroxyethyl metatoluidine, are dissolved in 50 parts of pyridine. 2.5 parts of 2-(2-chloro-2-cyanoethyl) benzoyl chloride are added slowly, then the mixture is heated at 40°-50° C. for 30 minutes. The dyestuff is salted out by simply diluting the mixture with 250 parts of water, acidifying the mixture by means of hydrochloric acid up to pH 3-4 and by the temperature being maintained at 10° C. to 15° C. The dyestuff thus obtained is identical with that in Example 8.

EXAMPLE 199

A fabric of ethylene glycol polyterephthalate fibres is printed with a printing paste containing 20 parts of the dyestuff of Example 11, 150 parts of a solid salt of sulphonated castor oil, 600 parts of a thickening agent and 250 parts of water. After being dried, the fabric is thermofixed for one minute at 200° C. and then subjected to a reducing treatment with sodium dithionate. A ruby shade having very good general fastness is obtained.

EXAMPLE 200

A fabric of ethylene glycol polyterephthalate fibres is foularded in a bath comprising 9 parts of the dyestuff of Example 100, 0.5 parts of a polyglycol ether of oleic alcohol, 1.5 parts of a polyacrylamide and 989 parts of water. After it has been dried, the fabric is thermofixed for one minute at 200° C. and then subjected to a reducing treatment with sodium dithionate. A violet shade is obtained with very good general fastness. 

We claim:
 1. Dyestuff of the formula: ##SPC15##in which m is equal to 0 or 1, n is equal to 1, 2 or 3, A represents the residue of an aromatic diazotisable amine devoid of solubilising acid groups, the benzene ring B is unsubstituted or substituted by one or two atoms of chlorine or bromine or methyl, ethyl, methoxy, ethoxy, or acylamino groups, X represents a hydrogen or chlorine atom or a methyl, ethyl, methoxy, ethoxy or acylamino group, Y represents a hydrogen atom or a methyl, ethyl, methoxy or ethoxy group, R is alkyl containing 1 to 4 carbon atoms, and Z represents a 2-cyanovinyl, 2-cyanoethyl or 2-chloro-2-cyanoethyl residue.
 2. Dyestuff as claimed in claim 1 wherein n is equal to
 2. 3. Dyestuff as claimed in claim 1 wherein A is substituted by alkylsulphonyl groups in which the alkyl residue contains 1 to 4 carbon atoms.
 4. Dyestuff as claimed in claim 1 wherein A is substituted by carbalkoxy groups in which the alkyl residue contains 1 to 4 carbon atoms.
 5. Dyestuff as claimed in claim 1 wherein m is zero, Y is hydrogen, X is hydrogen, chlorine, methyl or acetylamino, R is ethyl or β-cyanoethyl and n is
 2. 6. A dyestuff of the formula ##SPC16##in which A, m, n and Z are as defined in claim
 1. 7. Process for colouring hydrophobic materials in which the colouring agent is a dyestuff as claimed in claim
 1. 8. Hydrophobic materials which have been dyed or printed by a dyestuff as claimed in claim
 1. 9. Fibres or fabrics based on aromatic polyesters or cellulose triacetate dyed or printed with a dyestuff as claimed in claim
 1. 10. The dyestuff of the formula: ##SPC17##
 11. The dyestuff of the formula: ##SPC18##
 12. The dyestuff of the formula: ##SPC19## 